Annual Review of Analytical Chemistry - Volume 5, 2012

Laser-induced fluorescence (LIF) is a spectroscopic technique that involves the excitation of a molecular target by a beam of laser radiation followed by the detection of the subsequent emission of radiation from the target. LIF detection has several advantages over absorption spectroscopy. First, LIF has excellent detection sensitivity because a signal is observed against a dark background. Second, the emitted radiation can be collected at various angles with respect to the incoming laser beam, making it possible to obtain two- and three-dimensional images because the fluorescence is emitted in all directions. Third, by dispersing the fluorescence, it is also possible to learn about the transitions from the state excited to the various lower levels of the target species. Finally, because of the delay between the excitation and detection events, it is also possible to learn about what processes the excited target undergoes in the intervening time.

Hydrodynamic chromatography (HDC) has experienced a resurgence in recent years for particle and polymer characterization, principally because of its coupling to a multiplicity of physical detection methods. When coupled to light scattering (both multiangle static and quasi-elastic), viscometric, and refractometric detectors, HDC can determine the molar mass, size, shape, and structure of colloidal analytes continuously and as a function of one another, all in a single analysis. In so doing, it exposes the analytes to less shear force (and, hence, less potential for flow-induced degradation) than in, for instance, size-exclusion chromatography. In this review, we discuss the fundamental chromatographic underpinnings of this technique in terms of retention, band broadening, and resolution, and we describe the power of multidetector HDC with examples from the recent literature.

Traumatic brain injury (TBI) results from an event that causes rapid acceleration and deceleration of the brain or penetration of the skull with an object. Responses to stimuli and questions, loss of consciousness, and altered behavior are symptoms currently used to justify brain imaging for diagnosis and therapeutic guidance. Tests based on such symptoms are susceptible to false-positive and false-negative results due to stress, fatigue, and medications. Biochemical markers of neuronal damage and the physiological response to that damage are being identified. Biosensors capable of rapid measurement of such markers in the circulation offer a solution for on-site triage, as long as three criteria are met: (a) Recognition reagents can be identified that are sufficiently sensitive and specific, (b) the biosensor can provide quantitative assessment of multiple markers rapidly and simultaneously, and (c) both the sensor and reagents are designed for use outside the laboratory.

The number of applications using optical tomography has significantly increased over the past decade. A literature research providing this term as keyword gives 26 hits for 1990, 719 for 2000, and 9,202 for 2010. With an increasing number of applications, the number of different imaging modalities is also increasing. This review summarizes recent developments in tomographic methods for scattering and nonscattering samples. These two different cases of optical tomography are typically represented by biomedical imaging and atmospheric tomography, representing high- and low-scattering samples, respectively. An essential prerequisite for tomographic analyses is an understanding of light propagation in different media, which allows for the development of specific reconstruction algorithms for the different tomographic tasks.

New chemicals or drugs must be guaranteed safe before they can be marketed. Despite widespread use of bioassay panels for toxicity prediction, products that are toxic to a subset of the population often are not identified until clinical trials. This article reviews new array methodologies based on enzyme/DNA films that form and identify DNA-reactive metabolites that are indicators of potentially genotoxic species. This molecularly based methodology is designed in a rapid screening array that utilizes electrochemiluminescence (ECL) to detect metabolite-DNA reactions, as well as biocolloid reactors that provide the DNA adducts and metabolites for liquid chromatography–mass spectrometry (LC-MS) analysis. ECL arrays provide rapid toxicity screening, and the biocolloid reactor LC-MS approach provides a valuable follow-up on structure, identification, and formation rates of DNA adducts for toxicity hits from the ECL array screening. Specific examples using this strategy are discussed. Integration of high-throughput versions of these toxicity-screening methods with existing drug toxicity bioassays should allow for better human toxicity prediction as well as more informed decision making regarding new chemical and drug candidates.

The more nanotechnology develops, the more likely the release of engineered nanoparticles into the environment becomes. Due to a huge excess of natural nanoparticles, the identification and quantification of engineered nanoparticles pose a big challenge to analysts. Moreover, identification in a qualitative sense and quantification by mass concentration alone are not sufficient, because the potential environmental hazard arising from engineered nanoparticles is controlled by many other properties of the particles. We discuss the most important methods of fractionation and detection of both natural and engineered nanoparticles, with a focus on the chemical nature of the particles, particle concentration, and particle size. Analyses should not rely on only one method; instead, several complementary methods should, if possible, be used. Coupled techniques should be further developed and increasingly applied. Dedicated techniques that are tailored to the search for a particular sort of engineered nanoparticles are more promising than universal approaches that search for any engineered nanoparticles.

Within the past 15 years, compound-specific stable isotope analysis has continued to increase in popularity in the area of contaminant hydrology of organic molecules. In particular, in cases where concentration data alone are insufficient to elucidate environmental processes unequivocally, the isotope signature can provide additional unique information. Specifically, it can help answer questions about contaminant source apportionment, quantification of biotic and abiotic processes, and identification of transformation reactions on a mechanistic level. We review advances in laboratory and field investigations and exemplary applications in contaminant hydrology via stable isotope analysis. We also highlight future directions in the field.

Enzymatic biofuel cells represent an emerging technology that can create electrical energy from biologically renewable catalysts and fuels. A wide variety of redox enzymes have been employed to create unique biofuel cells that can be used in applications such as implantable power sources, energy sources for small electronic devices, self-powered sensors, and bioelectrocatalytic logic gates. This review addresses the fundamental concepts necessary to understand the operating principles of biofuel cells, as well as recent advances in mediated electron transfer– and direct electron transfer–based biofuel cells, which have been developed to create bioelectrical devices that can produce significant power and remain stable for long periods.

Nanoparticle toxicology, an emergent field, works toward establishing the hazard of nanoparticles, and therefore their potential risk, in light of the increased use and likelihood of exposure. Analytical chemists can provide an essential tool kit for the advancement of this field by exploiting expertise in sample complexity and preparation as well as method and technology development. Herein, we discuss experimental considerations for performing in vitro nanoparticle toxicity studies, with a focus on nanoparticle characterization, relevant model cell systems, and toxicity assay choices. Additionally, we present three case studies (of silver, titanium dioxide, and carbon nanotube toxicity) to highlight the important toxicological considerations of these commonly used nanoparticles.

Scanning ion conductance microscopy (SICM) is a versatile type of scanning probe microscopy for studies in molecular biology and materials science. Recent advances in feedback and probe fabrication have greatly increased the resolution, stability, and speed of imaging. Noncontact imaging and the ability to deliver materials to localized areas have made SICM especially fruitful for studies of molecular biology, and many examples of such use have been reported. In this review, we highlight new developments in the operation of SICM and describe some of the most exciting recent studies from this growing field.

Marine organisms have evolved extraordinarily effective adhesives that cure underwater and resist degradation. These underwater adhesives differ dramatically in structure and function and are composed of multiple proteins assembled into functional composites. The processes by which these bioadhesives cure—conformational changes, dehydration, polymerization, and cross-linking—are challenging to quantify because they occur not only underwater but also in a buried interface between the substrate and the organism. In this review, we highlight interfacial optical spectroscopy approaches that can reveal the biochemical processes and structure of marine bioadhesives, with particular emphasis on macrofoulers such as barnacles and mussels.

This article reviews recent work involving the development and application of nanoelectrodes in electrochemistry and related areas. We first discuss common analytical methods for characterizing the size, shape, and quality of nanoelectrodes, including electron microscopy, steady-state cyclic voltammetry, scanning electrochemical microscopy, and surface modification. We then emphasize recent developments in fabrication techniques that have led to structurally well-defined nanoelectrodes. We highlight recent advances in the application of nanoelectrodes in important analytical chemistry areas, such as single-molecule studies, single-nanoparticle electrochemistry, and measurements of neurotransmitters from single neuronal cells.

Physics-based simulation represents a powerful method for investigating the time-varying behavior of dynamic protein systems at high spatial and temporal resolution. Such simulations, however, can be prohibitively difficult or lengthy for large proteins or when probing the lower-resolution, long-timescale behaviors of proteins generally. Importantly, not all questions about a protein system require full space and time resolution to produce an informative answer. For instance, by avoiding the simulation of uncorrelated, high-frequency atomic movements, a larger, domain-level picture of protein dynamics can be revealed. The purpose of this review is to highlight the growing body of complementary work that goes beyond simulation. In particular, this review focuses on methods that address kinematics and dynamics, as well as those that address larger organizational questions and can quickly yield useful information about the long-timescale behavior of a protein.

Although stem cell fate is traditionally manipulated by exogenously altering the cells' extracellular signaling environment, the endogenous autocrine and paracrine signals produced by the cells also contribute to their two essential processes: self-renewal and differentiation. Autocrine and/or paracrine signals are fundamental to both embryonic stem cell self-renewal and early embryonic development, but the nature and contributions of these signals are often difficult to fully define using conventional methods. Microfluidic techniques have been used to explore the effects of cell-secreted signals by controlling cell organization or by providing precise control over the spatial and temporal cellular microenvironment. Here we review how such techniques have begun to be adapted for use with embryonic stem cells, and we illustrate how many remaining questions in embryonic stem cell biology could be addressed using microfluidic technologies.

Surface plasmon–coupled emission (SPCE) arose from the integration of fluorescence and plasmonics, two rapidly expanding research fields. SPCE is revealing novel phenomena and has potential applications in bioanalysis, medical diagnostics, drug discovery, and genomics. In SPCE, excited fluorophores couple with surface plasmons on a continuous thin metal film; plasmophores radiate into a higher–refractive index medium with a narrow angular distribution. Because of the directional emission, the sensitivity of this technique can be greatly improved with high collection efficiency. This review describes the unique features of SPCE. In particular, we focus on recent advances in SPCE-based analytical platforms and their applications in DNA sensing and the detection of other biomolecules and chemicals.

The past decade has seen an enormous increase in the number and breadth of imaging techniques developed for analysis in many industries, including pharmaceuticals, food, and especially biomedicine. Rather than accept single-dimensional forms of information, users now demand multidimensional assessment of samples. High specificity and the need for little or no sample preparation make Raman imaging a highly attractive analytical technique and provide motivation for continuing advances in its supporting technology and utilization. This review discusses the current tools employed in Raman imaging, the recent advances, and the major applications in this ever-growing analytical field.

The application of the recently developed synchrotron rapid scanning X-ray fluorescence (SRS-XRF) technique to the mapping of large objects is the focus of this review. We discuss the advantages of SRS-XRF over traditional systems and the use of other synchrotron radiation (SR) techniques to provide corroborating spectroscopic and diffraction analyses during the same analytical session. After reviewing routine techniques used to analyze precious specimens, we present several case studies that show how SR-based methods have been successfully applied in archeology and paleontology. For example, SRS-XRF imaging of a seventh-century Qur'ān palimpsest and an overpainted original opera score from Luigi Cherubini is described. We also review the recent discovery of soft-tissue residue in fossils of Archaeopteryx and an ancient reptile, as well as work that has successfully resolved the remnants of pigment in Confuciusornis sanctus, a 120-million-year-old fossil of the oldest documented bird with a fully derived avian beak.

Stimuli-responsive systems for the transport and delivery of materials to a given location at a specific time are highly valuable in numerous applications. The characteristics of the delivery system are dictated by the requirements of a particular application, which include the nature of the stimulus for actuation of the delivery process. Electron transfer has moved to the forefront as a stimulus for responsive delivery systems, particularly for those used in drug and reagent delivery, and for analyte transport/separation avenues. Interest in redox-activated delivery of materials arises from the abundance of redox-active stimuli that can be used to make delivery occur, the often simple chemical nature of the activation process, and the ease of constructing delivery vehicles with an integrated redox-responsive trigger group. This review is focused on vesicle- and micelle-based vehicles whose contents can be delivered by a redox stimulus due to their potential to meet the needs of key applications.

Digital microfluidics (DMF) is an emerging liquid-handling technology that enables individual control over droplets on an open array of electrodes. These picoliter- to microliter-sized droplets, each serving as an isolated vessel for chemical processes, can be made to move, merge, split, and dispense from reservoirs. Because of its unique advantages, including simple instrumentation, flexible device geometry, and easy coupling with other technologies, DMF is being applied to a wide range of fields. In this review, we summarize the state of the art of DMF technology from the perspective of analytical chemistry in sections describing the theory of droplet actuation, device fabrication and integration, and applications.